1, 4 diaminoanthraquinone compounds containing a carboxy-beta-tetrahydrofurfuryloxyalkylamide group in the 2-position



Patented Apr. 24, 1951 1,4 DIAMINOANTHRAQUINONE COMPOUNDS CONTAINING ACARBOXY-fl-TETRAHY- DROFURFURYLOXYALKYLAMIDE GROUP IN THE Z-POSITIONJoseph B. Dickey N. Y., assignors and Anthony Loria, Rochester, toEastman Kodak Company,

Rochester, N. Y., a corporation of New Jersey N Drawing. ApplicationNovember 1, 1947, Serial No. 783,624

7 Claims.

This invention relates to new 'anthraquinone compounds which are ofvalue to the dyeing or coloring art. The new compounds are particularlyof value for the dyeing of textile materials made of or containing acellulose carboxylic ester, in which ester the acid radical containsfrom two to four carbon atoms.

The. cellulose carboxylic esters which may be dyed or colored includethe hydrolyzed as well as the unhydrolyzed cellulose organic acid esterssuch as cellulose. acetate, cellulose propionate, or cellulose butyrateand the hydrolyzed as well as the unhydrolyzed mixed organic acid estersof cellulose such as cellulose acetate-propionate and celluloseacetate-butyrate. While our invention will be illustrated moreparticularly in connection with the coloration of cellulose acetate, amaterial to which our new dye compounds are especially adapted, it willbe understood that it applies to the coloration of other cellulosecarboxylic esters such as those just mentioned.

Much efiort has been devoted to the preparation of .dye compounds whichwill satisfactorily dye the aforesaid cellulose carboxylic ester textilematerials, especially cellulose acetate textile materials. We have foundnew anthraquinone compounds which color these materials blue shadeswhich possess good light and gas fastness properties.

It is, therefore, an object ofour invention to provide new anthraquinonecompounds. Another object of our invention is to provide new dyes bymeans'of which textile materials can be colored. A further object is toprovide colorations on textile materials which are of good fastness tolight,

gas, and washing. A specific object of our invention is to provide newanthraquinone compounds which color cellulose acetate textile materialsblue shades fast to light, gas, and wash ing. A still further object isto provide a satisfactory process for preparing the new compounds of ourinvention. Other objects will appear hereinafter.

The anthraquinone compounds by means of which the aforesaid objects areaccomplished or made possible may be represented by the general formula:

NIT-

I 2 wherein R. stands for a hydrogen atom, an alkyl group having one tofour, inclusive, carbon atoms, a hydroxyalkyl group having two to three,inclusive, carbon atoms, an alkoxyalkyl group having three to four,inclusive, carbon atoms, the tetrahydroiuriuryl group or the mo -pm Z 4)1-"CH2H H7,

group, and wherein n and m each represent the number one, two or three.

The anthraquinone compounds of our invention can be convenientlyprepared by reacting an amine having the formula:

wherein R has the meaning previously assigned to it with ananthraquinone compound having the formula:

wherein n has the meaning previously assigned to it, in the presence ofcuprous iodide and potassium acetate. The reaction can be carried out byheating together a mixture of the above materials under reflux atatmospheric pressure or under superatmospheric pressure in a closedreaction vessel such as an autoclave. Normally the reaction mixture isheated under reflux for approximately three hours. As a solvent anexcess of the amine, RNH2, or an inert diluent such as n-butanol orpyridine may be employed. When the reaction mixture has undergone therequired heating period it is cooled to room temperature and poured intoan excess of dilute hydrochloric acid. The precipitated dye compound isthen recovered by suction filtration, washed with water, and dried.

The following examples illustrate the anthraquinone compounds of ourinvention and their manner of preparation.

Example 1 10 grams of l-amino-4-bromoanthraquinone- Z-carboxy Btetrahydrofuriuryloxyethylamide are charged into an autoclave containingcc. of n-butanol, 25 cc. of 28% aqueous ammonia, 0.1 gram of cuprousiodide, and 2 grams of potassium acetate. The autoclave is sealed, andthe reaction mixture is heated at 160 C. for ten hours. When cool, theresulting clear blue solution is poured into 50 cc. of 9% hydrochloricacid to precipitate the dye compound which is recovered by filtration,washed with water, and dried. 1,4 diaminoanthraquinone-2-carboxy-[3-tetrahydrofurfuryloxyethylamide having the formula:

is obtained. It colors cellulose acetate textile materials blue shades.

Eaiample 2 grams of l-aminoA-bromoanthraquinone-2-carboxy-,9-tetrahydrofurfuryloxy-B-etho-xyethylamide are placed in anautoclave containing 100 cc. of n-butanol. cc. of aqueous methylamine,0.1 gram of cuprous iodide, and 2 grams of potassium acetate are thenadded and the autoclave is sealed. The reaction mixture is heated to 160C. and maintained at this temperature for ten hours. When cool, thecontents of the autoclave are poured into cc. of 9% hydrochloric acidwith stirring. The dye compound which precipitates is recovered byfiltration, washed with water, and dried. The resulting 1aminol-methylaminoanthraquinone- 2-carboxy 18tetrahydrofurfuryloxy-B-ethoxyethylamide colors cellulose acetate blueshades. It has the formula:

Example 3 10 grams of 1-aminoi-bromoanthraquinone-2carboxy-,8-tetrahydrofurfuryloxyethylamide, 10 cc. of a 30% aqueoussolution of methylamine, 0.5 gram of cuprous iodide, and 2 grams ofpotassium acetate are added to 50 cc. of pyridine. The reaction mixtureis heated under reflux on a steam bath for three hours with stirring.Upon cooling, the blue solution is poured into an excess of dilutehydrochloric acid and the precipitate formed is recovered by filtration,Washed with water, and dried. The 1-amino-4-methylaminoanthraquinone-2-carboxy-;3 tetrahydrofurfuryloxyethylamidethus obtained colors cellulose acetate blue shades. It has the for-Example 4 8.8 grams of 1-amino-4-bromoanthraquinone-2-carboxy-5-tetrahydrofurfuryloxyethylamide, 5 grams of52v-dihydroxypropylamine, 0.1 gram of 0 NH; g I H O o g I TCH2CH-CH:

on H

is obtained. It colors cellulose acetate blue shades.

- Example 5 9.7 grams of l-amino-4-bromoanthraquinone-2-carboxy-fi-tetrahydrofurfuryloxy-c-ethoxyethylamide, 5 grams ofethanolamine, 2 grams of potassium acetate, and 0.1 gram of cuprousiodide are heated together, with stirring, on a steam bath for 3 hours.When cool, the reaction mix ture is worked up in accordance with theprocedure described in Example 4.l-amino--B-hydroxyethylaminoanthraquinone 2carboxy-fltetrahydrofurfuryloxy-,8-ethoxyethylamide which has theformula:

is obtained. It colors cellulose acetate blue shades.

Example 6 9.7 grams of 1-amino-4-bromoanthraquinone-2-carboxy-e-tetrahydrofurfuryloxy-fi-ethoxyethylamide, 5 grams ofn-butylamine, 0.1 gram of cuprous iodide, and 2 grams of potassiumacetate are reacted together and worked up in accordance with theprocedure described in Example 4. l amino-4n-butylaminoanthraquinone-2-carboxy 5tetrahydrofurfuryloxy-S-ethoxyethylamide which has the formula:

is obtained. It colors cellulose acetate blue shades;

Example 7 10.6 grams of 1-amino-4-bromoanthraquinone- 2carboxy-fi-tetrahydrofurfuryloxy-fi-ethoxy-flethoxyethylamide, 5 gramsof fi-methoxyethylamine, 0.1 gram of cuprous iodide, and 2 grams ofpotassium acetate are reacted together and worked up in accordance withthe procedure described in Example 4.l-aminol-p-methoxyethylaminoanthraquinone Z-carboXy-[i-tetrahyedrofurfuryloxy ,8 ethoXy- S-ethoxyethylamide of1-amino-4=-bromoanthraquinone-2-carboxy-cwhich has the formula:tetrahydrofurfuryloxy-p-ethoxy-p ethoxyethyl- W NH gqqmcnzoons isobtained. It colors cellulose acetate blue amide, cc. of a 30% aqueoussolution of ethylshades. amine, 0.5'gram of cuprous iodide, 2 grams ofpo- Example 8 tassium acetate and 50 cc. of pyridine. The reactionmixture is reacted together and worked grams of -q up in accordance withthe procedure of Example 2 a 0 y-B- y u y y d 5 3. The1-arnino-4-ethylaminoanthraquinone-Z- grams ofB-tetrahydrofurfuryloxyethylamine,. 0.1 carboxy-p tetrahydrofurfuryloxyp3 ethoxy-pgram of cuprous iodide, and 2 grams of potasethoxyethylamidewhich is obtained colors cellusium acetate are reacted together andworked lose acetate blue shades. This dye has the forup in accordancewith the procedure of Example mula:

0 NH, II I reo en, c H CNGHQCHQOCHZCHQOGH2CHQOCHQCH 0H ll o o 4.1-aminc-4-c-tetrahydrofurfuryloxyethylami- I Example 11noanthraquinone-Z-carboky-B-tetrahydrofurfur yloxyethylamide which h sthe formulazf grams of lammo 4 bromoanthraqumone-2-carboxy-c-tetrahydrofurfuryloxyethylamide, 5 grams offl-eth-oxyethylamine, 0.1 gram of cuprous NR2 CH? 4 iodide, and 2 gramsof potassium acetate are rec 1r acted together and worked up inaccordance with e-'g the procedure of Example 4. The dye, l-amino- I o o4 8 ethoxyethylaminoanthraquinone 2 car- H2O CH2boxy-fl-tetrahydrofurfuryloxyethylamide which II I has the formula: oN-CHQCH2--OOHZ H H2 7 H O NH! I 0 2% H2C--GH1 O- l-CH CH -OCH2( 3H isobtained. It colors cellulose acetate blue shades. y \O/ Example 9 \C/9.7 grams of 1-amino-4-bromoanthraquinone- 1| L o r q EH11 2-carboxyfl-tetrahydrofurfuryloxy {3 ethoxyf: U O O a ethylamide! 5 grams oftetrahydrofurfurylamineI is obtained. It colors cellulose .acetate blue0.1 gram of cuprous iodide, and 2 grams of potasshadea sium acetate arereacted together and worked up in accordance with the procedure ofExample 4. Example 12 The 1-amino-4-tetrahydrofurfurylaminoanthragramsof 1 4 m m x -fl f tetrahydltofurfuryloxy B- 2-carboxy3-tetrahydrofurfuryloxyethylamide,' 5 ethoxyethylamine which is obtainedcolors cellugrams of -hydroxypropylamine 1 gram of lose acetate blueshades. It has the formula: cuprous i dide, and 2 grams or" potassiumacetate 7 are reacted together and worked up in accordance 0 NH, withthe procedure described in Example 4. The 11 I H flzoflfimz resultingLamina-4 v hydroxypropylaminoan- CNGH2CHO-CHzCHz-O-OHz-(JH 0Bthraquinone-Z carboxy-B-tetrahydrofurfuy1oxy- I ethylamide colorscellulose acetate blue shades. The dye has the formula:

1 HgCCH o NHZ H I H2C---CH9 N-CH 'H 011, 7 o H 1 (E H r o-NoH,oHZ-o-oi1H H,

Example 10 C/ I l A suitable autoclave is charged with 10.6 grams V (g-QH2CH2CHFOH 7 Emample 13 10.6 grams of l-amino-4-bromoanthraquinone-2-carboxy-p-tetrahydrofurfuryloxy fi-ethoxy-[iethoxyethylamide, 5 gramsof ,o-hydroxyethylamine, 0.1 gram of cuprous iodide, and 2 grams ofpotassium acetate are reacted together and worked up in accordance withthe procedure described in Example 4. The resulting l-amino-4-fi-hydroxyethylaminoanthraquinone 2-carboxyfi-tetrahydrofurfuryloxy-fiethoxy ,8 ethoxyethylamide colors cellulose acetate blue shades. The dyehas the formula:

wherein n has the meaning previously assigned to it. The reaction iscarried out by adding the finely divided acid chloride to an aqueoussolution containing a slight excess of the amine. With thoroughagitation the reaction mixture is warmed to 60 to 70 C. and maintainedat this temperature for a short time. When cool, the

product is recovered byfiltration, washed with water, and dried.

l-amino-4-bromoanthraquinone-2 carboxylic acid chloride is prepared bytreating l-aminoanthraquinone-2-carboxylic acid first with bromine innitrobenzene and then with thionyl chlo- 1 ride in the following manner.

grams of 1-aminoanthraquinone-2-carboxylic acid chloride are slurried in100 grams of dry nitrobenzene and heated to 100 C. At this temperature6.5 grams of bromine in grams of nitrobenzene are added to the reactionflask over a period of ten minutes. The temperature is raised rapidly to200 C. and maintained at this point for only a short time followingwhich the reaction mixture is allowed to cool to 100 C. 10 grams ofthionyl chloride are added to the flask, and heating at 100 C. iscontinued until no more hydrogen chloride gas escapes. Normally, thiswill require approximately two hours. When cool, the1-amino-4-bromoanthraquinone- 2-carboxylic acid chloride formedcrystallizes out and is recovered by filtration, washed with ether, anddried. When immersed in a pre-heated melting point bath the compoundshows a melting point of 218 to 220 C.

Amines having the formula:

can be prepared by aminating alcohols having the formula:

Dickey and A. R. Gray. The procedures employed in Examples XIX, XX, XXI,or XXII of this patent may be applied to the production of any of theamines herein employed to produce the compounds of our invention.

Alcohols having the formula specified in the preceding paragraph can beprepared in accordance with the process described in U. S. Patent2,196,748, issued April 9, 1940, to J. B. Dickey.

The anthraquinone compounds of our invention are, for the most part,relatively insoluble in water and, accordingly, they may beadvantageously directly applied to the material in the form of anaqueous suspension which can be prepared by grinding the dye to a pastein the presence of a sulfonated oil, soap, or other suitable dispersingagent and dispersing the resulting paste in water.

Direct dyeing operations are ordinarily carried out by immersing thematerial to be dyed or colored in the aqueous suspension at atemperature of 45-55 C. following which the temperature is raised to75-85 C. The duration of immersion depends on the depth of shadedesired, a long immersion producing a deep coloration and a shorterimmersion yielding a weaker shade. The weight of dye employed also isgoverned by the depth of coloration desired. In general l-3% by weightof dye to material is used. Upon completion of the dyeing operation thematerial is removed, washed with soap, rinsed, and

ried.

While the use of the compounds of our invention has been illustrated inconnection with the dyeing of cellulose acetate rayon, it will beunderstood that the other materials named herein can be substituted forthe cellulose acetate rayon and the dyeing operation carried out in themanner described. Again, while the colors yielded by the dye compoundshave been given with reference to cellulose acetate rayon, ordinarilygenerally similar colors are obtained on textile materials made of theother cellulose carboxylic esters indicated herein. The dye compounds ofour invention also possess some utility for the coloration of wool,nylon and silk textile materials. They may be applied to these materialsby the method described above or by any other suitable known method usedfor the dyeing of these materials.

9 10 We claim: 4. The anthraquinone compounds having the 1. Theanthraquinone compounds having the formula: formula: I 0

0 wherein n represents a number selected from the E group consisting ofone, two and three.

, 5. The anthraquinone compound having the formula: wherein R representsa member selected from the O 2 group consisting of a hydrogen atom, analkyl 15 1 H2O CH2 group having one to four, inclusive, carbon atoms, ftH v 1 1 a hydroxyalkyl group having two to three, in- E c1usive,carbonatoms and an alkoxyalkyl group 0 0. having three to four, inclusive,carbon atoms and wherein n represents a number selected from the 0 groupconsisting of one, two and three.

2. The anthraquinone compounds having the The anthraqumone p u havmg tformula: v formula:

7. The anthraquinone compound having the formula:

wherein R represents an alkyl group having one 35 f NEE to four,inclusive, carbon atoms and n represents o H H A} A} a number selectedfrom the group consisting of E 9 one, two and three. 0

3. The anthraquinone compounds having the formula: 40,

O NH: JOSEPH B. DICKE-Y.

l]; HgC-CH1 H I ANTHONY LORIA.

C-N-(CzH4O),,-CH H E, it 45 REFERENCES CITED The following referencesare of record in the file of this patent:

' UNITED STATES PATENTS Number Name Date wherein R represents ahydroxyalkyl group hav- 2,176,437 Runne et a1 Oct. 17, 1939 ing two tothree, inclusive, carbon atoms and n 2,242,760 Schoeller et a1 May 20,1941 represents a number selected from the group 2,372,663 Dickey etal.Apr. 3, 1945 consisting of one, two and three. 2,383,236 Buckley Aug.21, 1945

1. THE ANTHRAQUINONE COMPOUNDS HAVING THE FORMULA